KR100458419B1 - Dyeing composition of fiber-reactive dye - Google Patents

Abstract

The present invention is one or two of one or more vinylsulfonyl dye and having the general formula _{(A) -SO 2 -CH 2 -CH} 2 -N (R) water-soluble dye composition containing at least one dye having at the -VX ( Wherein the dye having a vinylsulfonyl group and the dye having a group of the general formula (A) are present in a ratio of from 90:10 mol% to 60:40 mol%), and one or two vinylsulfonyl or β- A water-soluble dye composition comprising at least one water-soluble dye having a tosylsulfonyl group and an amino compound represented by the following formula (3), wherein the dye having a vinylsulfonyl and / or a? -Sulfatoethylsulfonyl group has a structure represented by the following formula 100: 10% to 100: 40% by mol).

(3)

In the above equations,

R is hydrogen or alkyl of 1 to 4 carbon atoms and may be interrupted by one or two heteroatoms and may be substituted by sulfo, carboxy, hydroxy, sulfato, phosphato and / or lower alkanoylamino and, V is a covalent bond, alkylene having 2 to 4 carbon atoms, or the formula _{-CO-NH-CH 2 -CH 2} - group, and the;

X is a water-soluble group.

These dye compositions are suitable for dyeing synthetic polyamide fibers, in particular synthetic polyamide fibers in the form of fine fibers, especially polyamide fibers having an amino end group of at least 60 gram equivalents per 1000 kg of polyamide polymer.

Description

Dyeing composition of fiber-reactive dye

The present invention relates to the technical field of fiber-reactive dyes.

Methods for dyeing wool with a sulfo-containing dye having a fiber-reactive beta -sulfatoethylsulfonyl group are known. This method is a staining method in which a wooly fabric is dyed in a dye solution for 30 minutes or more at a boiling temperature while maintaining the pH of the dye solution at 6 to obtain a desired wet fastness and brightness. However, it is very difficult to maintain the pH at 6 for dyeing. When the pH is higher than 6, the structure of the wooly fabric is easily damaged. On the other hand, when the pH is lower than 6, the wet fastness and brightness of the dye are noticeably decreased do. As a solution to this, use of the vinylsulfonyl derivative thereof instead of the? -Sulfatoethylsulfonyl dye, which is the method disclosed in US Pat. No. 3,082,837, provides a dye having a satisfactory level of wet fastness at pH 5 It was possible to do. The vinylsulfonyl derivative used in this method was prepared by adding trisodium phosphate to an aqueous solution of β-sulfatoethylsulfonyl dye at 80 ° C., neutralizing the resulting solution, and adjusting the pH to 5 with acetic acid . However, this method also has a fatal disadvantage that a large amount of dye precipitates in an alkaline aqueous medium when the water-soluble β-sulfatoethylsulfonyl group is converted into a vinylsulfonyl group. According to the technique disclosed in U.S. Patent No. 3,082,837, the solubility of the dye can be significantly improved. However, this is not necessarily the case. In the process of converting the? -Sulfatoethylsulfonyl dye into the vinylsulfonyl dye, the secondary aliphatic amine containing a sulfo group or a carboxy group is preferably used in an amount of from 1.5 times to 4 times the? -Sulfatoethylsulfonyl group It was only possible if it existed in an excess molar ratio of the boat.

Conventional methods for dyeing synthetic polyamide fiber materials require a long time at boiling temperature to salt large amounts of the bath to the fiber because the rate of dyeing of the bath is very slow. Therefore, the fixation of the dye is made after such a long time of dyeing. According to the conventional method, since most of the dyeing bath is present in a non-solidified state, the dye is not properly fixed on the fiber. As a result, the obtained dyes not only have poor color clarity and uniformity of salt but also show an improper fastness.

In order to solve the above-mentioned disadvantages, attempts have been made to dye synthetic polyamide fiber materials with dyes containing fiber-reactive groups of vinyl sulfone in a bath of weakly acidic pH 3 to 4 (U.S. Patent No. 4,762,524). This method comprises reacting a dye having a β-sulfatoethylsulfonyl group with a secondary alkylamine having a sulfo group or a carboxyl group (present in a molar ratio of 50 to 100% based on β-sulfatoethylsulfonyl group dye) , And partially converting the β-sulfatoethylsulfonyl dye into a β- (alkylamino) ethylsulfonyl dye while treating the dyes in aqueous solution with an alkaline reagent such as trisphosphate at a pH of about 9 and at about 90 ° C. And then adjusting the pH of the mixture to 3 to 4, whereby the dyeing of the synthetic polyamide fiber material takes place at boiling temperature. However, this method has a disadvantage that dye is insufficiently penetrated into modern fiber materials containing fibers composed of very fine filaments, in addition to having unsatisfactory uniformity of salinity and distinctive barriness. In this regard, the dyes known in the continuous dyeing processes present a serious problem that the hue changes at the early and late stages of dyeing.

Therefore, there is still a need to improve the dyeing method of synthetic polyamide fiber materials.

In the present invention, a novel preparation (composition) effect, s. Melliand Textilber. 70, 360-364 (1989)), but with high fastness and evenness. These dye formulations (A) (hereinafter also referred to as "formulations (A)") comprise a dye of formula (1) as defined below and a dye of formula (2) as defined below having the same dye radical F as in formula , And mixtures of dyes of different formula 2, such as two or three, with the same dye radicals F as in formula (I), wherein the dyes of formula (1) and the dyes of formula (2) _{- (SO 2 -CH = CH 2} ) n and _{- [SO 2 -CH 2 -CH 2} -N (R) -VX] n , each group 90 to the reference: it is 40%, preferably 10% to 60 80: 20% to 65: 35%.

The present invention also relates to a dye mixture comprising one or more (e.g. two or three) dyes of the formula (IA) as defined below and / or one or more (e.g. two or three) 2 or 3), wherein the dye of formula (1A) and formula (1) and the compound of formula (3) are present in a ratio of 100: 10% to 100: 1 relative to one another on the basis of the? - sulfatoethylsulfonyl and vinylsulfonyl groups, (B) (hereinafter referred to as " Formulation (B) ") which contains the dyeing agent (B) at a molar equivalent ratio of 40: 40%, preferably 100: 20% to 100: 35%.

The preparation (B) according to the invention preferably has only one amino compound of formula (3), preferably one or more dyes of formula (1A)

[Chemical Formula 1]

(2)

≪ EMI ID =

(3)

In the above equations,

F is a mono-, di- or polyazo dye (e.g. trisazo dye), or a heavy metal complex mono-, dis- or trisazo dye, or anthraquinone, azomethine, phenazine, stilbene, triphenylmethane, As radicals of dyes, such as santene, thioxanthene, nitroaryl, naphthoquinone, perylenetetracarbimide, formazan, copper formazan, phthalocyanine, copper phthalocyanine, nickel phthalocyanine or cobalt phthalocyanine dyes, - having one or two groups which impart solubility (for example, sulfato, sulfo and / or carboxy groups, preferably one or two sulfo groups, particularly preferably one sulfo group);

n is 1 or 2, preferably 1;

M is hydrogen or an alkali metal (e.g., sodium, potassium, or lithium);

R is hydrogen or alkyl having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, which may be interrupted by one or two heteroatoms, such as -O- and -NH-, and is optionally substituted with one or more substituents selected from the group consisting of sulfo, carboxy, Alkanoylamino of 2 to 5 carbon atoms, preferably R is hydrogen, more preferably methyl, ethyl or beta -hydroxyethyl; R < 2 >

V is a covalent bond, C 1 -C 4 alkylene (e.g. methylene, and ethylene), or -CO-NH-CH ₂ -CH ₂ of the group;

X is a water-solubilizing group such as carboxy, sulfo, sulfato, phosphato or hydroxy.

Examples of the -N (R) -VX group in the dye of formula 2 include N-methyl-N- (β -sulfoethyl) -amino, N, N-di- (β- (? - carboxyethyl) amino, N-methyl-N- (? - carboxyethyl) Pentyl) -amino and N-ethyl-N- (? - carboxypropyl) -amino.

Preferably, the dye radical F, containing one or two sulfato, sulfo and / or carboxyl groups, is a radical of a mono- or disazo dye, or a heavy metal complex azo dye, for example a 1: 2 chromium complex, 2, more preferably a radical of an o, o'-1: 1 copper complex monoazo or disazo dye, or a radical of anthraquinone or copper formazan or nickel phthalocyanine or copper phthalocyanine dye or triphendioxazine dye to be.

The radical F may contain substituents and groups commonly used in organic dyes. Examples thereof include alkyl groups having 1 to 4 carbon atoms (e.g., methyl, ethyl, propyl, isopropyl, and butyl, preferably ethyl, more preferably methyl); An alkoxy group having 1 to 4 carbon atoms (e.g., methoxy, ethoxy, propoxy, isopropoxy and butoxy, preferably ethoxy, more preferably methoxy); Alkanoylamino groups having 2 to 5 carbon atoms (e.g., acetylamino group and propionylamino group); A benzoylamino group which may be substituted by the aforementioned groups which impart methyl, ethyl, methoxy, ethoxy, chlorine and / or water-solubility; Primary and / or disubstituted amino groups (the substituents are alkyl groups having 1 to 4 carbon atoms and / or phenyl groups such as monoalkylamino and dialkylamino groups having 1 to 4 carbon atoms in the alkyl radical, phenylamino or N- (C ₁ -C ₄ -alkyl) -N-phenyl-amino groups, wherein the alkyl radicals are as defined above for the phenyl and / or water-solubility groups such as hydroxy, sulfato, sulfo and carboxy, (For example, sulfophenyl), which phenyl group may also be substituted by a group mentioned above which imparts chlorine, methyl, methoxy and / or water-solubility and a substituent having such a group (e.g. methylamino, ethylamino, Amino, isopropylamino, butylamino, N, N-di (? - hydroxyethyl) amino, N, N-di (? - sulfatoethyl) amino, sulfobenzylamino, N, ) Amino and diethylamino, phenylamino and sulfophenylamino groups) An alkoxycarbonyl group having an alkyl radical having 1 to 4 carbon atoms (e.g., methoxycarbonyl and ethoxycarbonyl), an alkylsulfonyl group having 1 to 4 carbon atoms (e.g., methylsulfonyl and ethylsulfonyl Halogen atoms such as fluorine, chlorine, and bromine, which may be mono- or disubstituted by alkyl having 1 to 4 carbon atoms, wherein the alkyl radical is, for example, phenyl and naphthyl, Or a carbamoyl group which may be substituted with a group described above which imparts water-solubility such as hydroxy, sulfato, sulfo, and carboxy, or a substituent having such group (for example, sulfophenyl), such as N-methyl Carbamoyl and N-ethylcarbamoyl, a sulfamoyl group which may be mono- or di-substituted by an alkyl group having 1 to 4 carbon atoms and an N-phenyl-N-alkylsulfamoyl group (These alkyl groups may also be the same as described above Which may be substituted by a group (e.g., hydroxy, sulfato, sulfo and carboxy) and / or by a phenyl, or by a substituent having such a group (e.g. sulfophenyl) But are not limited to, methylsulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl, N-isopropylsulfamoyl, N-butylsulfamoyl, N- (? - hydroxyethyl) sulfamoyl and N, Hydroxyethyl) sulfamoyl; N-phenylsulfamoyl, ureido, hydroxy, and sulfomethyl groups.

The vinylsulfonyl and beta -sulfatoethylsulfonyl groups present in the dyes of formula (1A), (1) and (2) and the group of formula (3a) may be directly attached to the dye chromophore substituent of the dye radical F or the aromatic nucleus of the dye chromophore.

Examples of other substituents or other groups in the radical F are groups of the formulas:

[Chemical Formula 4]

[Chemical Formula 5]

In the above equations,

R < ⁰ > is hydrogen or alkyl having 1 to 4 carbon atoms (e.g., methyl and ethyl);

R ¹ is hydrogen or alkyl having 1 to 4 carbon atoms (e.g., ethyl and methyl), alkanoyl having 2 to 5 carbon atoms and / or a group as described above for imparting water-solubility (e.g., carboxy, hydroxy, sulfo, Phthaloyl and phosphato);

R ² is either one of the meanings of R ¹ or a cycloalkyl of 5 to 8 carbon atoms (such as cyclohexyl), or an alkyl of 1 to 4 carbon atoms (such as ethyl and methyl), an alkoxy of 1 to 4 carbon atoms Methoxy, and ethoxy), chlorine and / or water-soluble groups (such as sulfo and carboxy), which may be substituted by one or two substituents selected from the group consisting of:

The -NR ¹ R ² group is a saturated heterocycle radical having from 5 to 8 carbon atoms which may contain one or two heteroatoms, such as the group of -O- or -NH-, for example N-morpholino, Lt; RTI ID = 0.0 > N-piperazino < / RTI >radical;

W is a C 3-8, preferably 3-8, carbon atoms which may be interrupted by one or two heteroatoms such as phenylene or alkylene of 2 to 4 carbon atoms (e.g., ethylene and n-propylene), or groups of -O- or -NH- (E.g., ethyleneoxyethylene or ethyleneaminoethylene) having 4 to 6 carbon atoms, alkylenephenylene having an alkylene radical having 1 to 4 carbon atoms, or alkylene radicals having 1 to 4 carbon atoms, such as ethylene And propylene), or phenyl having 3 to 8, preferably 4 to 6, carbon atoms, which may be interrupted by one or two heteroatoms, such as the group of -O- or -NH-, (C ₁ -C ₄ ) alkylene-phenylene (C ₁ -C ₄ ) -alkylene wherein the phenylene group has from 1 to 4 carbon atoms (such as methyl and ethyl) and from 1 to 4 carbon atoms Alkoxy < / RTI > (e.g., ethoxy and methoxy) and the aforementioned groups which impart water-solubility Carboxy) additionally it may be substituted) by one or two substituents selected from the group consisting of a;

Z is a vinylsulfonyl or beta -sulfatoethylsulfonyl group as shown in formula 1, 1A and 2, or a group of formula 3a:

[Chemical Formula 3]

Wherein R, V and X are the same as described above.

In the above-described formulas and the formulas described below, in the case of having different meanings and having the same meaning, the individual constituents shown in the formulas may represent the same or different meanings within the defined category.

"Sulfo "," carboxy ","phosphato",and" sulfato "include both acid or salt forms thereof. Therefore, the sulfo group is -SO ₃ M, the carboxyl group is -COOM, the phosphato group is -OPO ₃ M ₂ , and the sulfato group is -OSO ₃ M (wherein M is as defined above).

Examples of preferred mono-and disazo dyes of formula (1) include dyes of the following formula (6a, 6b and 6c) and heavy metal complexes derived therefrom (e.g., 1: There are 6e dyes:

[Chemical Formula 6a]

[Formula 6b]

[Chemical Formula 6c]

[Chemical formula 6d]

[Formula 6e]

In the above equations,

D ¹ , D ² , D ³ , D ⁴ , E, K ¹ , K ² and K ³ are as defined above;

K is a divalent radical of the coupling component but in each dye D ¹ , D ² , D ³ , D ⁴ , K ¹ , K ² , K ³ and K are sulfato , Sulfo and / or carboxy groups, preferably one or two sulfo groups, particularly preferably one sulfo group;

v is 0 or 1;

Z is a vinylsulfonyl, a? -Sulfatoethylsulfonyl group or a group of the above formula (3a).

Preferred dyes of formula (1) also include disazo dyes of formula (6f): < EMI ID =

(6f)

In this formula,

M, n and Z are as defined above;

D has the meaning of D ¹ or D ² , respectively, depending on whether the radical Z is bonded to D or not.

Radicals D ¹ and ZD ^{2 which} are components of aromatic amines which may have the function of a diazo component are radicals of the following formulas 7a and 7b and D ³ and ZD ⁴ radicals are radicals of the following formulas 8a and 8b:

[Formula 7a]

[Formula 7b]

[Chemical Formula 8a]

[Formula 8b]

In the above equations,

R ^G is hydrogen, sulfo, carboxy, the general formula Y-SO ₂ -W ^o - or Y ^o -SO ₂ -W ^o -, wherein Y is vinyl or β-sulfatoethyl and Y ⁰ is a radical of formula _{) -CH 2 -CH 2 -N (R} ) -VX ( where R, V and X is a group of the same as defined above), W ^o is a covalent bond, alkylene of 1 to 4 carbon atoms (e.g., methylene, ethylene , And n-propylene), or an alkylene of 3 to 8, preferably 4 to 6, carbon atoms which is interrupted by one or two heteroatoms selected from the group consisting of -O- and -NH-, or phenylene methylene or phenylene Ethenylene);

P ¹ is selected from the group consisting of hydrogen, sulfo, methyl, ethyl, methoxy, ethoxy, alkanoyl having 2 to 5 carbon atoms such as acetyl and propionyl, cyano, alkoxycarbonyl having 2 to 5 carbon atoms, Carbonyl, N- (C ₁ -C ₄ -alkyl) carbamoyl, fluorine, chlorine, bromine or trifluoromethyl;

P ² is selected from the group consisting of hydrogen, methyl, ethyl, methoxy, ethoxy, cyano, nitro, chlorine, alkanoylamino of 2 to 5 carbon atoms (eg acetylamino), alkoxycarbonyl of 2 to 5 carbon atoms Carbonyl and ethoxycarbonyl), carbamoyl, N- (C ₁ -C ₄ -alkyl) sulfamoyl, sulfophenylamidocarbonyl, phenylamidocarbonyl, alkylsulfonyl having 1 to 4 carbon atoms, phenyl Sulfonyl or phenoxy;

m is 0, 1 or 2, provided that when m is 0, this group is a hydrogen atom;

M is as defined above;

The benzene ring of formulas (7a) and (7b) may additionally contain a hydroxy group at the ortho position with respect to the free bond leading to the azo group.

Among the meanings of the groups defined above, P ¹ is preferably hydrogen, sulfo, methyl, methoxy, fluorine or chlorine, and P ² is preferably hydrogen, methyl, methoxy or acetylamino.

ZD ² - is also derived from a diaminobenzene or diaminonaphthalene compound and is a compound of the following formulas (9a) and (9b):

[Formula 9a]

[Formula 9b]

In the above equations,

P ¹ , P ² , M and m are as defined above;

R ^B is a group of formula (4) or (5) as defined above.

The radical E which is a component of the couplable and diazotizable aromatic amino compound of the general formula HE-NH ₂ can be a radical of the following formulas 10a, 10b and 10c:

[Chemical Formula 10a]

[Chemical Formula 10b]

[Chemical Formula 10c]

In the above equations,

P ¹ , M and m are as defined above;

P ³ is selected from the group consisting of hydrogen, alkyl of 1 to 4 carbon atoms such as methyl or ethyl, alkoxy of 1 to 4 carbon atoms such as methoxy and ethoxy, chlorine, alkanoylamino of 2 to 5 carbon atoms, And propionylamino), benzoylamino, ureido, phenylureido, alkylureido wherein the alkyl radical has 1 to 4 carbon atoms, phenylsulfonyl or alkylsulfonyl of 1 to 4 carbon atoms.

Examples of groups of the general formulas (7a) and (7b) without the general formula -SO ₂ -Y or -SO ₂ -Y ⁰ include the following: phenyl, 2-methylphenyl, 3- and 4-methylphenyl, 2-methoxyphenyl , 3- and 4-methoxyphenyl, 2- chlorophenyl, 3- and 4-chlorophenyl, 2,5-dichlorophenyl, 2,5-dimethylphenyl, 2-methoxy- 3-, and 4-sulfamoylphenyl, 2-, 3- and 4- (N-methylsulfamoyl) phenyl, ) -, - (N-ethylsulfamoyl) -, - (N, N-dimethylsulfamoyl) 2-carboxyphenyl, 3-carboxyphenyl, 3-chloro-6-carboxyphenyl, 2-carboxyphenyl, 2- Sulfophenyl, 3-sulfophenyl, 4-sulfophenyl, 2,5-disulfophenyl, 2,4-disulfophenyl, 3,5-disulfophenyl, -5-sulfophenyl, Methoxyphenyl, 5-sulfo-2-ethoxyphenyl, 4-sulfo-2-methoxyphenyl, 2-methoxy- Carboxy-4-sulfophenyl, 2,5-dimethoxy-4-sulfophenyl, 2,4-dimethoxy-5-sulfophenyl, 2 2-sulfo-4-methylphenyl, 2-methyl-4-sulfophenyl, 2-chloro-4-sulfophenyl, 2 Dichloro-4-sulfophenyl, 2-sulfo-4- and 5-chlorophenyl, 2-sulfo-4,5-dichloro Phenyl, 2,5-dichloro-6-sulfophenyl, 2,5-dichloro-4-sulfophenyl, 2- Methoxy-4-sulfophenyl, 2,4-dimethoxy-6-sulfophenyl, 2-sulfo-5-acetylamino-4 Methylphenyl, 2-methyl-4,6-disulfophenyl, 2,5-disulfo-4-methoxyphenyl, 2-sulfo-5-nitrophenyl, 3-acetylamino-2-sulfophenyl, 4-acetylamino-2-sulfophenyl, 4-sulfonaphthyl, 4-acetylamino- Sulfonaphth-1-yl, 7-sulfonaphth-1-yl, 8-sulfinaphth-1-yl, 1-yl, 3,6-disulfo-and 5,7-disulfonaphth-1-yl, 3,7-disulfonaphth-1-yl, 2-yl, 6,8-disulfonaphth-2-yl, 1,6-disulfonaphth-2-yl, 2-yl, 3,6-disulfonaphth-2-yl, 4,8-disulfonaphth-2-yl, 4-sulfophenyl, 2-hydroxy-3,5-disulfophenyl, 2-hydroxy-5-acetylamino-3- 3-acetylamino-4-sulfophenyl, 2-hydroxy-5-chloro-4-sulfophenyl, 2-hydroxy-5-methylsulfonylphenyl, 2-hydroxy- -Nitro-4-sulphonaph 1-yl and 1-hydroxy-4,8-disulfonic Estepona soft-2-yl.

Examples of groups of the above formulas (7a) and (7b) having the general formula -SO ₂ -Y or -SO ₂ -Y ⁰ group are the following: 2- (β-sulfatoethylsulfonyl) phenyl, 3- (Β-sulfatoethylsulfonyl) phenyl, 2-chloro-3- (β-sulfatoethylsulfonyl) phenyl, 4- (2-bromo-4- (? - sulfatoethylsulfonyl) phenyl, 2-chloro-4- Phenyl, 4-chloro-3- (p-sulfatoethylsulfonyl) phenyl, 2-ethoxy-4- or 5- (p-sulfatoethylsulfonyl) Methoxy-5-or 4- (p-sulfatoethylsulfonyl) phenyl, 2,4- (Β-sulfatoethylsulfonyl) phenyl, 2,4-dimethoxy-5- (β-sulfatoethylsulfonyl) phenyl, 2,5-dimethoxy- Sulfatoethylsulfonyl) phenyl, 2-methoxy-5-methyl-4- (beta -sulfato (棺 -sulfatoethyl) phenyl, 2-sulfo-4-vinylsulfonylphenyl, 2- (Β-sulfatoethylsulfonyl) phenyl, 6-carboxy-1-sulfato naphth-2-yl, 5- Naphth-2-yl, 6- (棺 -sulfatoethylsulphonyl) naphth-2-yl, 6- or 7- or 8- (Β-sulfatoethylsulfonyl) -6-fluoro-2- (4-fluorophenyl) Ethyl] phenyl, 3- or 4 - [? - (? '- sulfatoethylsulfonyl) ethylamino Phenyl], 4 - [? - (? - sulfatoethylsulfonyl) ethylamino] -2- or 3-sulfophenyl, 4- - [? - (? '- sulfatoethylsulfonyl) propylamino] -2- or 3-sulfophenyl, 4- [? - (?' - sulfatoethylsulfo 2-carboxyphenyl and amino derivatives thereof (which are? -Sulfatoethylsulfonyl groups or? -? - sulfatoethylsulfonyl groups) [Beta] - [N-methyl-N- (beta '-sulfoethyl) -amino] ethylsulfonyl, [beta] - [ Amino] -ethylsulfonyl or? - [N, N-di- (? '- hydroxyethyl) -amino] ethylsulfonyl group.

Examples of the partial general formula D ¹ -N = NE- and ZD ² -N = NE- groups include 4- (4'-sulfophenyl) azo-2-sulfophenyl, 4- (2 ', 4'- Azo-2-methoxy-5-methoxyphenyl, 4- (4 ', 8'-disulfonaphth- Azo-3-acetylaminophenyl, 4- (4'-sulfophenyl) azo-6-sulfonaphth-1-yl, 4- [ Phenyl] azo-3-methylphenyl, 4- [4 '- (? - sulfato 3-ureidophenyl, 4- [6 '- (? - sulfatoethylsulfonyl) naphth-2'-yl] 2'-methoxy-5'-p-sulfatoethylsulfonyl) phenyl] azo-8-hydroxy-6-sulphonaphth-3-yl.

Examples of the diaminobenzene and diaminonaphthalene compounds, which are some elements or constituents of the above general formulas (9a) and (9b), include 1,4-phenylenediamine, 2-sulfo-1,4-phenylenediamine, 2- Sulfone-1,4-diaminonaphthalene, 8-sulfo-2,6-diaminonaphthalene, 1,3-phenylenediamine, 4-sulfo-1,4-phenylenediamine and 6 - sulfo-1,4-diaminonaphthalene.

Examples of the groups belonging to the groups of the formulas 10a, 10b and 10c include 3-methyl-1,4-phenylene, 3-methoxy-1,4-phenylene, , 2,5-dimethyl-1,4-phenylene, 3-ureido-1,4-phenylene, 3-ureido- Phenylene, 2-methyl-5-acetylamino-1,4-phenylene, 2-methoxy-5-acetyl Amino-1,4-phenylene and 2-sulfo-5-amino-phenylene in which the 4 position of the phenylene radical is connected to the azo group to represent the radical D ¹ or D ² , 6-sulfo-, 7- Sulfo- and 8-sulfonaphth-4,1-ylene (the four positions of which are bonded to the azo group of the radical E), 8-hydroxy-6-sulfonaphth-7,2-ylene, -6-sulfonaphth-7,3-ylene and 8-hydroxy-4,6-disulfonaphth-7,3-ylene where the 7-position is connected to the azo group to form the radical E.

The radicals K ¹ and -K ² -Z, which are coupling elements of the general formula HK ¹ or HK ² -Z, are the radicals of the formulas (11a) to (11k)

[Chemical Formula 11a]

[Formula 11b]

[Chemical Formula 11c]

[Chemical Formula 11d]

[Chemical Formula 11e]

[Formula 11f]

[Chemical Formula 11g]

[Chemical Formula 11h]

[Formula 11j]

[Chemical Formula 11k]

In the above equations,

R ^G , P ¹ , P ² , m and M are as defined above;

R ^H is hydrogen, W ^o -SO ₂ -Y or W ^o -SO ₂ -Y ^o , or a group of Formula 4 or Formula 5;

P ⁴ is alkanoylamino having 2 to 5 carbon atoms (such as propionylamino, especially acetylamino), or a substituent selected from the group consisting of chlorine, methyl, methoxy, sulfo and carboxy and / or W ^o -SO _2- Y or W ^o -SO ₂ -Y ^o wherein Y, Y ^o and W ^o are as defined above, or a phenylureido which may be substituted by a group of the above formula (4) or (5) by a group of chlorine, methyl, methoxy, a nitro, sulfo, and carboxy group substituent selected and / or defined in the consisting of -SO ₂ -Y or W ^o W ^o -SO ₂ -Y ^o substituents or formula 4, or 5 Benzoylamino which may be substituted;

P ⁵ is hydrogen, alkyl having 1 to 4 carbon atoms (e.g., methyl and ethyl), alkoxy having 1 to 4 carbon atoms (e.g., methoxy and ethoxy), fluorine, chlorine, or sulfo;

P ⁶ is selected from the group consisting of hydrogen, alkyl having 1 to 4 carbons such as methyl and ethyl, alkoxy having 1 to 4 carbons such as methoxy and ethoxy, chlorine, alkanoylamino having 2 to 7 carbons such as acetylamino And propionylamino), ureido or phenylureido;

P ⁷ is hydrogen or alkyl having 1 to 4 carbon atoms, which may be substituted by hydroxy, cyano, carboxy, sulfo, sulfato, methoxycarbonyl, ethoxycarbonyl or acetoxy;

P ⁸ is hydrogen or alkyl having 1 to 4 carbon atoms which may be substituted by hydroxy, cyano, carboxy, sulfo, sulfato, methoxycarbonyl, ethoxycarbonyl or acetoxy, or phenyl (C 1 -C 4 alkyl, C 1 -C 4 alkoxy, chlorine and / or the above-mentioned -SO ₂ -Y or W ^o W ^o -SO ₂ -Y ^o group, or the formula (4) or general formula (5) of the Lt; / RTI >group);

P ⁹ is selected from the group consisting of hydrogen, alkyl of 1 to 4 carbon atoms (e.g. methyl), cyano, carboxy, carbalkoxy of 2 to 5 carbons (e.g. carbomethoxy and carboethoxy), carbamoyl, Preferably methyl, carboxy, methoxycarbonyl, ethoxycarbonyl or phenyl, more preferably methyl or carboxy;

T is a benzene or naphthalene ring, preferably a benzene ring;

P ¹⁰ is preferably hydrogen, alkyl having 1 to 4 carbon atoms (such as methyl), alkoxy having 1 to 4 carbon atoms (such as methoxy) or alkyl having 1 to 4 carbon atoms substituted by cyano, Alkyl having 1 to 4 carbon atoms or phenyl;

P ¹¹ is hydrogen, chlorine, bromine, sulfo, carbamoyl, methylsulfonyl, phenylsulfonyl, cyano or sulfoalkyl having 1 to 4 carbon atoms, preferably hydrogen, sulfo, or an alkyl radical having 1 to 4 carbon atoms (For example, sulfomethyl), cyano or carbamoyl;

B is alkylene having 1 to 4 carbon atoms which may be substituted by sulfo, hydroxy, phosphato, sulfato and carboxy, or alkylene having 1 to 4 carbon atoms which is substituted by methylene phenylene, ethylene phenylene, phenylene methylene, phenylene ethylene or phenylene, Or methylenephenylene, which may be substituted in the benzene radical by fluorine, chlorine, bromine, methyl, methoxy, cyano, sulfo, carboxy, acetyl, nitro, carbamoyl and / or sulfamoyl, Or the radical -BR ^G is hydrogen;

D is a radical of the above general formula (7a), (7b), (9a) or (9b).

Also, the radicals -K ¹ and -K ² -Z are groups of the following formulas (12a) to (12h):

[Chemical Formula 12a]

[Chemical Formula 12b]

[Chemical Formula 12c]

[Chemical Formula 12d]

[Chemical Formula 12e]

(12f)

[Chemical Formula 12g]

[Chemical Formula 12h]

In the above equations,

P ¹ , P ² , P ⁹ , P ¹⁰ , P ¹¹ , B, T, M, m and D have the same meanings as mentioned above, particularly preferred meanings;

Z ^o is hydrogen in K ¹ ;

The radical Z has the abovementioned meaning in K ² or a group of the above formula 4 or 5;

R ^c is amino or a group of the above formula (4) or (5).

-KH radical in the formula 6e as a radical of the general formula of any one of the meaning of the above radicals K ^1, or the general formula 11b, 11c or 11k W ^o -SO ₂ -Y or W ^o -SO ₂ -Y ^o Or a group of the above formula (4) or (5), or a group of the above formula (12b) or (12c) wherein R ^c is amino.

In Formulas 11a, 11b and 12a, the free bond leading to the azo group is bonded to the aromatic nucleus at the ortho position with respect to the hydroxyl group.

Examples of K ^{1 in} the above general formulas (11) and (12) include 1-hydroxynaphth-2-yl, 2-hydroxynaphth-1-yl, 6- and 7-sulfo-2-hydroxynaphth- 2-hydroxy-6,8-disulfonaphth-1-yl, 4-sulfo-1-hydroxynaphth-2-yl, Disulfo-1-hydroxynaphth-2-yl, 1-amino-3-methylphen-4-yl, 1-amino- 1-aminophen-4-yl, 3-acetylamino-1-aminophen-4-yl, 2,5-dimethyl- Amino-6-sulfonaphth-4-yl, 1-amino-8-sulfonaphth-4-yl, Amino-5,7-disulfonaphth-1-yl, 1-amino-8-hydroxy-6-sulfanaphth- 2-yl, 1-amino-8-hydroxy-2,4-disulfonaphth-7-yl, 1-hydroxy- 8-hydroxy-3,6- and 4,6-di Amino-8-hydroxy-6-sulfonaphth-7-yl, 3-acetylamino-8-hydroxy- Amino-8-hydroxy-6-sulfone, 8-hydroxy-6-sulfinaphth-7-yl, 2-amino-8-hydroxy-3,6-disulfonaphth-7-yl, 2-acetylamino-8-hydroxy-6-sulfanaphth- Amino-8-hydroxy-3,6-disulfonaphth-7-yl, 4-amino-8- - and 4,6-disulfonaphth-7-yl, 1-amino-8-hydroxy-3,6- and -4,6-disulfonaphth-2-yl, 1-acetylamino- (4'-aminobenzoyl) -8-hydroxy-3,6- and -4,6-disulfonaphth-2-yl, Yl, 1- (3'-aminobenzoyl) -8-hydroxy-3,6- and -4,6-disulfonaphth-7-yl, 1-phenyl- Yl, 1- (4'-sulfophenyl) -3-methyl-5-hydroxy (2 ', 5'-disulfophenyl) -3-methyl-thiazol-4-yl, 1- 4-yl, 1- (4'-methyl-4'-sulfophenyl) -3-carboxy-5-hydroxypyrazol- Yl) -3-methyl-5-hydroxypyrrazol-4-yl, 1- (5 ', 7'-disulfonaphth-2'- (2 ', 5'-dichloro-4'-sulfophenyl) -3-methyl-5-hydroxypyrazol-4-yl, 4-methyl- Methyl-6-hydroxypyrid-2-on-4-yl, 1-N-ethyl-3-sulfo Methyl-6-hydroxypyrid-2-one-4-yl, 1-N-ethyl-3-carbamoyl- 1-yl, 1- (2'-methoxy-5'-methyl-4'-sulfophenyl) Aminocarbonyl) -2-oxoprop-1-yl, 1-amino-8-hydroxy-7- (4'-sulfophenylazo) -3,6-diseponaphth- -8-hydroxy-7 - (2 ', 5'-disulfophenylazo) -3,6-disulfonaphth-7-yl and 2-hydroxy-6-carboxynaphth-1-yl [ (Wherein R ^o is preferably hydrogen), 1- [4 '- (? - sulfatoethylsulfonyl) phenyl] -3-methyl-5-hydroxypyrazole- 4-yl, 1- [2'-methoxy-5'-methyl-4 '- (βsulfatoethylsulfonyl) phenyl] (2-methoxy-5'-methyl-4 '- (? - sulfatoethylsulfonyl) phenylaminocarbonyl] -2-oxoprop-1-yl and 1-amino- Sulfoethylsulfonyl) phenylazo] -3,6-disulfonaphth-2-yl, and also the? -Sulfatoethylsulfonyl group is a vinylsulfonyl group or a group represented by the formula Substituted by a sulfonyl group (e.g.,? - [N-methyl-N- (β'-sulfoethyl) amino] ethylsulfonyl or β- (N-methyl-N-carboxymethyl) ethylsulfonyl group of 3a There is a type of radical mentioned above.

In the above formulas 6d and 6e having a metal complex-bonded oxygen atom, the radical K < ³ > is a radical of the following formulas 13a to 13e:

[Chemical Formula 13a]

[Chemical Formula 13b]

[Chemical Formula 13c]

[Chemical Formula 13d]

[Chemical Formula 13e]

In the above equations,

Groups of formula are as defined above;

R ^D is a radical Z or R ^{B as} defined above;

R ^E is a radical R ^B or R ^{H as} described above.

Examples of phthalocyanine dyes include the following dyes:

[Chemical Formula 14]

In this formula,

P _c is a nickel radical or preferably copper phthalocyanine;

R ^A is an amino group of the formula -NR ¹³ R ¹⁴ wherein R ¹³ and R ¹⁴ are each independently hydrogen or alkyl having 1 to 4 carbon atoms which may be substituted by hydroxy or sulfo, A heterocyclic N-containing radical, such as a piperidino radical;

R < ¹² > is hydrogen or alkyl having 1 to 4 carbon atoms (e.g., methyl and ethyl);

G ² is phenylene which may be substituted by one or two substituents selected from the group consisting of alkyl of 1 to 4 carbon atoms (such as ethyl and methyl), halogen (such as bromine and chlorine), carboxy and sulfone, Sulfophenylene), or alkylene having 2 to 6 carbon atoms (e.g., ethylene);

a is a number from 0 to 2;

b is a number from 0 to 3;

c is a number of 1 or 2, the sum of a, b and c is 2 to 4;

Z ¹ is vinylsulfonyl,? -Sulfatoethynylsulfonyl or a group of the above formula (3a) or (5).

Phthalocyanine dyes include, among others, dyes of the following formulas (14a) and (14b):

[Chemical Formula 14a]

[Chemical Formula 14b]

In the above equations,

M and Z < ¹ > are as defined above;

a is a number of 1 or 2;

b is a number from 0 to 2;

c is a number of 1 or 2, the sum of a, b and c is 2 to 4;

Pc is a nickel radical or preferably copper phthalocyanine;

alk is alkylene having 2 to 4 carbon atoms, preferably ethylene.

Examples of copper-formaldehyde dyes include the following formula 15:

[Chemical Formula 15]

In this formula,

Z ¹ and n are as defined above;

X ¹ is an oxygen atom, or preferably a carbonyloxy group of -COO-;

P ₁ and P ₂ are each independently a benzene or naphthalene ring, the nitrogen atom on P ₁ and X ₁ are in ortho position relative to each other, the oxygen and nitrogen atoms on P ₂ are in ortho position with respect to each other, Or naphthalene nucleus may also be substituted by one or more substituents selected from the group consisting of halogen (e.g. chloro), nitro, alkyl of 1 to 4 carbon atoms (e.g. methyl and ethyl), alkoxy of 1 to 4 carbon atoms (e.g. methoxy and ethoxy), sulfamoyl, Which is unsubstituted or substituted by one or two substituents selected from the group consisting of lower alkyl, lower alkoxy, lower alkoxy, lower alkoxy, lower alkoxy, lower alkoxy, lower alkoxy, And preferably P < ¹ > and P < ₂ > are both a benzene ring;

P ₃ represents a straight or branched alkylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, which may be substituted by sulfophenyl group, or 1 or 2 groups selected from the group consisting of methyl, ethyl, methoxy, ethoxy and chlorine A phenylene group or a naphthalene group which may be substituted with one or more substituents, preferably a benzene ring;

T ¹ , T ² and T ³ are each independently sulfo or carboxy, preferably sulfo;

e, f, g are each independently 0, 1 or 2 and their sum is from 1 to 4, preferably 2 or 3, more preferably 2, and, in the case of e or f or g is 0, T ^1, or T ² or T ³ groups are each a hydrogen atom;

Z ¹ is bonded to an aromatic radical P ₁ , P ₂ or P ₃ , preferably P ₂ .

Copper-formaldehyde dyes are especially those in which P ₁ and P ₂ are both benzene rings, Z ¹ is bonded to P ₂ , T ¹ and T ² are each sulfo, and e and g are both 1.

When Z ¹ is bonded to P ₁ , e is 0, g is 2, and T ² is sulfo. Preferably, also -P ^₃ - (T _{3) f} is a radical phenyl radical or a 2-or 4-sulfophenyl.

Of the copper-formaldehyde dyes, in particular the dyes of the following formula (15a) are important:

[Chemical Formula 15a]

In this formula,

M and Z < ^{1 >} have the abovementioned meaning, particularly preferred meanings;

R < ²⁰ > is hydrogen or sulfo.

An example of a triphendioxazine dye is a dye of formula 16: < RTI ID = 0.0 >

[Chemical Formula 16]

In this formula,

Benzene two sulfo on ring -SO ₃ M is present in preferably an ortho position relative to the oxygen atom of a heterocyclic ring;

M and Z are as defined above;

B ^o is an oxy-O-, or preferably an amino group -NH-;

A ^o may be interrupted by 1 or 2 hetero groups (e.g., a hetero group selected from -O-, -NH-, -NH-CO- and -CO-NH) and / Alkylene of 2 to 6 carbon atoms which may be substituted by sulfato or carboxy, or cyclohexylene;

p is 0 or 1;

An example of a triphendioxazine dye is a dye of the formula:

[Chemical Formula 17]

In this formula,

M and Z are as defined above;

A is alkylene having 2 to 4 carbon atoms;

A ^o is the same as defined in the above formula (16);

p is 0 or 1;

Q is sulfo, carboxy or sulfato.

Examples of anthraquinone dyes are those of formula 18:

[Chemical Formula 18]

In this formula,

M, Z and p are as defined above;

Ph is selected from the group consisting of alkyl having 1 to 4 carbon atoms such as methyl and ethyl, alkoxy having 1 to 4 carbon atoms such as methoxy and ethoxy, halogen such as chlorine and bromine, Or phenylene which may be substituted by two substituents, or phenylene substituted by 3 or 4 methyl groups.

The dyes of formulas (1) and (1A) are known in a number of documents as described in U.S. Patent Nos. 4,336,190, 4,492,654, 4,046,754, 4,577,015, 3,359,286, 3,268,548 and 3,385,843. The dyes of formula (2) and their preparation are disclosed in U.S. Patent No. 3,802,837.

Similarly, the amino compounds of formula (3) are known. Examples thereof include N-methyl-N- (β -sulfoethyl) -amine (methyltaurine), N, N-di- (β -hydroxyethyl) (? -Carboxypropyl) -amine, N-ethyl-N- (? - carboxypropyl) N- (β-carboxyethyl) -amine, N-ethyl-N- (β-carboxyethyl) -amine and N-methyl-N- (ω-carboxypentyl) -amine.

The dye of formula (2) can be obtained by reacting the dye of formula (1) with an amino compound of formula (3). For example, a vinylsulfonyl group and an amine of the formula (3) are added to the dye of the formula (1) in an aqueous solution, the reaction is carried out at a pH of from 7 to 9 and a temperature of from 25 to 50 ° C, The synthesis solution is neutralized and adjusted to a pH of 4 to 7, preferably 5.5 to 6.5 by using an organic acid or an inorganic acid (for example, hydrochloric acid, acetic acid or phosphoric acid) according to the method, and then the solution is precipitated with an electrolyte salt such as sodium chloride and potassium chloride Salting out) or by spray-drying the synthesis solution.

The dye of formula (2) is prepared by adding an amine of formula (3) to the dye of formula (1A) in an aqueous solution in an amount of animal and animal, preferably an aqueous solution of an alkali inorganic compound such as sodium hydroxide, sodium carbonate Or trisphosphate) is added to adjust the pH to 8.5 to 13, preferably 9 to 12.5, particularly preferably 9 to 10.5, maintaining this level during the reaction, and maintaining the temperature at 20 to 100 DEG C, preferably 80 to 95 Lt; 0 > C for about 5 to 15 minutes. The intermediate formed from the beta -sulfatoethylsulfonyl dye of formula (1A) is the vinylsulfonyl dye of formula (2). The reaction time should not be substantially exceeded as much as possible and is about 5 minutes at a reaction temperature of 88 to 92 占 폚 and at a pH of 9 for 5 to 10 minutes, at a reaction temperature of 20 to 25 占 폚 and at a pH of 12 to 12.5. When the reaction temperature is in the range of pH 9 to 10 and the reaction temperature is 40 to 60 ° C, the reaction is terminated after about 15 minutes.

The dyeing agent according to the invention may be present in the form of a solid, such as a powder or granules, or in the form of a liquid such as an aqueous solution. They can be prepared in a conventional manner by mixing the respective components, for example the dyes of formulas 1 and 2, or the dye (s) of formulas 1 and / or 1A, and the amines of formula 3, have. The dyeing agent (A) containing the dyes of the formulas (1) and (2) can be obtained by adding an alkaline compound (for example the abovementioned compound) and an amine of the formula (3) to 1 mole of the dye (s) of the formula , Or dyes of the formula (1) and / or the dyes of the formula (1A), and amines of the formula (3) are mixed in water with the ratio according to the invention, i.e., in equimolar amounts, based on the? -Sulfatoethylsulfonyl group and the vinylsulfonyl group, Particularly preferably at a pH of from 8.5 to 13 and at a temperature of from 20 to 100 < 0 > C. When the dye mixture containing the dyes of formulas (1) and (2) is formed, the alkali synthesis solution as described above is neutralized to a pH of 4 to 7 and the dye mixture according to the present invention is spray-dried or isolated from the synthesis solution by salting out .

The solid dye formulations and their aqueous solutions contain electrolytic salts such as sodium chloride, potassium chloride or sodium sulfate, as in the usual and usual case of water-soluble dyes, which are derived from precursors, It was introduced into the formulation at the time of separation. The dyeing agent may additionally contain conventional auxiliaries used for dyeing or stabilizing the fiber material with a fiber-reactive dye, and examples of the auxiliary agent include a solubility improver (containing formaldehyde and alkyl and containing , The condensation product has a molecular weight of 5,000 to 15,000 and a degree of sulfonation of 80 to 150%), a humectant, a drying agent, an antifungal agent, a defoaming agent and a smoothing agent. The dyeing preparation (B) of the present invention may also contain an alkali agent such as sodium carbonate or trisodium phosphate in an amount necessary for dyeing at this stage.

The dyes according to the invention, comprising the dyes of the formulas 1 and 2 or the dyestuffs of the formulas 1 and / or 1A and the amines of the formula 3, can be used as caramels, such as natural amide fibers (for example, Lt; / RTI > is suitable for dyeing radiation-containing fibrous materials. They have many advantages and are particularly suitable for dyeing synthetic polyamide fibers. Using the dyeing agent of the present invention, it is possible to obtain dyes having excellent color strength, high level of saltiness, high brightness and high definition color tone. In addition, the dyes obtained using the dyes according to the invention have a significantly improved color, especially on synthetic polyamide fibers, compared to dyes obtainable with dyestuffs and dyestuffs conventionally used so far And fastness properties, and the dyed fibers exhibit a very high level of saltiness and dye penetration.

Examples of synthetic polyamide fibers (nylons) that can be dyed to exhibit specific advantages by using the formulations of the present invention include nylon 6 (polycaproamide), nylon 6,6 (polyhexamethyleneadipamide), nylon 7 (Polyenaminamide), nylon 6,12 (polyhexamethylene dodecamid), nylon 11, nylon 12, and copolyamides of nylon 6,6 or nylon 6, such as hexamethylenediamine, epsilon -caprolactam And polymers made from adipic acid and adipic acid, polymers made from hexamethylenediamine and isophthalic acid, or polymers made from adipic acid, hexamethylenediamine and 2-methylpentamethylenediamine or 2-ethyl-tetramethylenediamine It is a fiber made of polymer. Nylon 6 containing 15% by weight or less, preferably 0.5 to 15% by weight of polyhexamethylene isophthalamide or poly (2-methyl) pentamethylene adipamide or poly- (2-ethyl) tetramethylene adipamine, 6, and further copolyamides of nylon 6 containing up to 15%, for example 0.5 to 15% by weight of nylon 6,6, are preferred.

The dyeing agent according to the invention can be used particularly advantageously for dyeing microfibers of synthetic polyamides. Dyeing these microfibers shows high salt intensities and dye permeability. Microfibers refer to multifilaments (prepared by melt spinning) fibers consisting of filaments having individual filament fineness of less than or equal to 1 denier (1.1 dTex) (Chemiefasern / Testilind, 94, 877-800 (1982) Properties and Production of Micro Filament Yarns ").

The fiber materials of nylon 6 and nylon 6,6 having an amine end group of at least 60, such as 60 to 100, particularly preferably 70 g equivalents per 1000 kg of synthetic polyamide, especially nylon fiber, Advantages and significantly improved dyeings. Among these, particularly preferred polyamide fibers are fibers containing 85% by weight or more of polyhexamethylene adipamide or 85% by weight or more of poly-caproamide. Also provided is a polyamide fiber material comprising 85% by weight or more of polyhexamethylene adipamide and 15% by weight or less, for example 0.5 to 15% by weight of polyhexamethylene isophthalamide, a polyamide product of isophthalic acid and hexamethylene diamine, Particularly suitable.

These fiber materials having an amino end group content of not less than 60 g equivalents have a relative viscosity of 40 to 60, preferably more than 45, as measured in aqueous formic acid having a strength of 90% at 20 占 폚.

In addition to separating the carboxamide bridges by conventional hydrolysis in the polymer formed, in order to obtain a high proportion of the free aminomethane group in the polymer or polyamide fibers, excess diamines (e.g., hexamethylenediamine) Terminal amino group of at least 60 g equivalents (for example, 60 to 100 g equivalents), preferably 70 or more, and more preferably 75 g equivalents per 1,000 kg of polyamide fibers used in the present invention is obtained have. Examples of the diamines to be used include hexamethylenediamine, 2-methyl-pentamethylenediamine, 2-ethyl-tetramethylenediamine, 1,3-diaminotoluene and 1,4-bis (aminomethyl) cyclohexane.

These types of polyamide polymers and polyamide fibers are shown in Examples B-1 to B-3 to be described later.

The amide fiber material may be used in conventional structural form, e.g., in the form of a yarn. The yarn form may also take the form of a twill or a wound package or a woven or knitted fabric or a decorative fabric such as carpets and ornaments. The amide fibers may also be mixed with other synthetic fibers, such as polyurethane fibers (e.g., spandex) and / or cellulose fibers (e.g., cotton).

The dyeing agents according to the invention can be used to dye polyamide fiber materials having an amino end group content of from 70 to 95, preferably from 70 to 85 or from 75 to 90 g equivalents per 1000 kg of polymer (polyamide fibers) have. As described above, the dyeing agents of the present invention are useful not only for textile materials made of high quality synthetic polyamides but also for textile materials made of high quality synthetic polyamides, especially those having a density of less than or equal to 4 denier (4.4 dTex), especially less than or equal to 2.2 dTex, It is also possible to provide high quality dyeing of fibers (made by the melt spinning method) consisting of filaments with individual filaments having a fineness of less than 1 denier (1.1 dTex), for example 0.8 denier (0.88 dTex).

The use of the dyeing agents according to the invention for dyeing and printing the above-mentioned fiber materials, in particular synthetic polyamide fiber materials, can be carried out according to the usual known printing and dyeing procedures. For example, from an aqueous dye liquid by a dyeing method at 40 to 130 DEG C, or by padding a fibrous material with a dye liquid or by spraying onto a dye liquid, and then heat-treating the impregnated material at a temperature of about 80 to 130 DEG C For example, saturated high-temperature steam or microwave treatment). In general, dye fixation of fiber materials containing amide groups takes place at a pH of from 3 to 7.5, preferably from 3.5 to 7, particularly preferably from 5.5 to 6.5.

When the dyeing preparation (B) according to the present invention is used as a starting material, the dyeing process is carried out by first adding an alkaline reactive agent (for example, sodium hydroxide, sodium carbonate or trisodium phosphate) to the aqueous dye solution containing the preparation (B) The pH of the mixture is adjusted to 8.5 to 13, preferably 9 to 10.5, and the solution is heated at 60 to 100 DEG C, preferably at 80 to 95 DEG C for about 10 minutes After adjusting the pH to 3.5 to 7, preferably 5.5 to 6.5, the dyeing liquid is diluted with water according to the characteristics of the dyeing procedure to be used, if necessary, the fibrous material is added, To continue dyeing. In the case of the dyeing method, the dyeing is carried out at 40 to 110 ° C, preferably 60 to 95 ° C for 40 to 90 minutes, the dyeing temperature is adjusted to 40 to 60 ° C, and the pH is adjusted to 10 to 30 minutes by using an alkaline agent (sodium carbonate) 11 and dyeing is continued for about 15 minutes at the same temperature and copper pH range and the resulting dyeings are rinsed in the usual manner, for example with water, in a bath containing a non-ionic detergent at 80 DEG C , Rinse with a water bath containing a small amount of acetic acid, rinse with cold water and warm water, and then dry.

When dyeing a fibrous material using a padding or printing method, a possible method is to first make a thick aqueous solution of the dyeing agent (B), adjust the pH to 3.5 to 7 by alkaline treatment as described above, and add the necessary auxiliaries ) And the resulting padding liquid or printing paste is applied to the fibrous material and the padded or printed fibrous material is heat treated at 80 to 130 DEG C for about 15 minutes by means such as hot air, saturated high temperature steam or microwave irradiation Over-pad or over-sprayed with an alkaline aqueous solution containing sodium hydroxide, sodium carbonate, trisodium phosphate or sodium silicate, and heat-treated at about 60 캜 to 100 캜 for about 15 minutes. The dyes produced in this way are finished in the usual manner as described above.

Preferably, the fiber material is subjected to a dyeing method such that the ratio of fiber material: dye liquid is 1: 40 to 1: 3 in the above-described pH and temperature range (i.e., a temperature range of pH 3.5 to 7 and 40 to 110 ° C) Dye. In the case of a fiber tuft, for example, in a jar of 1: 3 to 1:10 in a jigger, or in a pot for a woven and knitted fabric in a pot at a ratio of 1:10 to 1:40, preferably 1:10 to 1 ≪ / RTI >: 20. For example, firstly, about 5 to 10% by weight of an alkaline reagent (for example, sodium hydroxide, sodium carbonate or trisodium phosphate) in solid form or in the form of an aqueous solution is added to the aqueous solution of the dyeing agent (B) , The pH is adjusted to 9 to 11 and the salt bath is heated at 60 to 95 캜, preferably at 80 to 90 캜, and maintained at this temperature and selected pH for about 10 to 15 minutes The pH is then adjusted to 3.5 to 7, preferably 4 to 6.8, more preferably 5.5 to 6.5, and the pH is adjusted to 30 (Salt bath) is heated at 80 ° C to 100 ° C for 15 to 20 minutes, and then the dye solution (salt bath) is irradiated at about 40 ° C in the dye solution The dyeing is continued for 45 to 60 minutes, the temperature of the liquid or the salt bath is lowered to 60 DEG C, the pH is adjusted to 10 to 11, preferably 10.5 with an alkaline reagent (such as sodium carbonate), and at 60 DEG C for about 15 minutes After continuous dyeing, the dyed fibrous material is rinsed and finished in the manner described above.

When staining a fiber material with a dyeing agent (A) containing the dye of the formulas (1) and (2), it is not necessary to pre-treat the agent aqueous solution with an alkali. The dyeing process in the dyeing process is carried out, for example, by the following procedure: The fiber material is introduced into the aqueous dye solution (dye bath) of the dyeing preparation (A) , The salt bath is maintained at 40 to < RTI ID = 0.0 > 80 C < / RTI > to 100 C for about 30 to 40 minutes and then the dyeing is continued for 45 to 60 minutes at the same temperature , The dye solution (salt bath) is cooled to 60 DEG C according to the above-described manner, the pH is adjusted to 10 to 11, the dyeing is continued for about 15 minutes, and the dyed material is then finished in the manner described above.

The dyeing preparation (A) can be used similarly to the above in a padding or printing process. In these cases, the preferred procedure is to add an aqueous padding liquid or printing paste of the dyeing agent (A) at a pH of from 3.5 to 7, preferably from 4 to 6.8, more preferably from 5.5 to 6.5, to the fiber material, in particular the woven or knitted fabric To fix the dye, the fiber material is heat treated at 80-130 ° C for 15 minutes by means of hot air, saturated high-temperature steam or microwave irradiation, impregnated or printed with a dye, and then an aqueous alkali solution For example, sodium hydroxide, sodium carbonate, trisodium phosphate or sodium silicate) is over-padded or over-sprayed and the heat treatment is continued for about 15 minutes at about 60-100 ° C. The dyed material in this way is finished in the usual manner as described above.

The following examples illustrate the present invention. Here, parts and percentages are based on weight unless otherwise specified, and parts by weight have the same relationship as kg to l.

Example 1

26 parts (= 46 molar equivalents) of the dye of formula A and 1.5 parts (9.2 molar equivalents) of N-methyltaurine sodium salt were dissolved in 20 parts of a solution of 7 parts of trisodium phosphate in 1000 parts of water. The resulting dye solution has a pH of about 10. The mixture was heated to a temperature of about 90 ° C., kept at the same temperature for about 10 minutes, adjusted to pH 5.5 with aqueous acetic acid having a strength of 60%, and supplemented with water to make 5000 parts skin.

(A)

To 20 parts of the dye raw material, 100 parts of skin was added to the skin by adding water containing about 0.1% of a commercial humectant. This bath was added to 10 parts of fabric prepared from the nylon fiber of Example B-1 to be described later, the pH of the bath was adjusted to 5.5 with acetic acid, and then the bath was heated to 98 DEG C steadily for 30 minutes, The process was allowed to proceed at the same temperature for 45 minutes, the bath was cooled to 60 ° C, the pH was adjusted to 10.5 with a concentrated aqueous sodium hydroxide solution, and maintained at this pH and 60 ° C for 15 minutes. The dyed fabric is then drained and the dyed fabric is rinsed in a conventional manner, that is to say the fabric is rinsed with cold water, washed in an aqueous bath containing a non-ionic detergent at 80 DEG C and then again in a bath containing a small amount of acetic acid at 40 DEG C Rinsed in cold water, rinsed in cold water, and centrifuged to dryness.

A dyed product having excellent color strength with a clear and distinct golden yellow hue was obtained. This staining also showed a much better level of salt balance than when using dye (A) alone, but also had a darker, sharper, and higher color intensity.

Example 2

Twenty-four parts (= 38 molar equivalents) of the dye solution of the following formula (B) in 1000 parts of water are mixed with 60 parts of a 10% strength aqueous solution of tri-sodium phosphate. The mixture was heated to 85 DEG C and held at this temperature until the pH was about 9.2, stirred for about 5 minutes, then 2.14 parts (= 13.3 molar equivalents) of sodium salt of N-methyltaurine was added and stirred Continue for about 3 minutes, adjust the pH to about 6 using acetic acid, cool the mixture to room temperature and add water to make 5000 parts by volume.

[Chemical Formula B]

20 parts of this raw material solution was diluted with 80 parts of water, and this bath was added to 10 parts of the yarn made of the polyamide fiber described later in Example B-1. The fabric was initially stirred at a temperature of 20 DEG C for 5 minutes and then the bath was heated to 90 DEG C for 30 minutes and the dyeing process was continued at the same temperature for 45 minutes during which the pH was maintained at about 5.5 with dilute aqueous acetic acid, pH 10 and 60 < 0 > C for 10 minutes. Then, the dyeing was drained and the dyed fabric was finished in the same manner as in Example 1.

A dyed product with excellent color strength is obtained with a clear and distinct bright yellow hue and a high level of saltiness.

On the other hand, when the procedure of Example 2 was carried out in accordance with known methods without addition of N-methyltaurine, the resulting dye exhibited inadequate uniformity of salinity and an unqualified yellowish hue.

Example 3

a) To 24 parts (= 38 molar equivalents) of the dye solution of formula (B) in 1000 parts of water was added 120 parts of a 5% aqueous solution of trisodium phosphate. The mixture is heated to a temperature of about 85 占 폚 and maintained at the same temperature until the pH is 9.2. Thereafter, the mixture was stirred for about 5 minutes, 1.84 parts (11.4 molar equivalents) of sodium salt of N-methyltaurine was added, stirring was continued for about 3 minutes, the pH was adjusted to about 6 using acetic acid, Followed by spray drying. A dye powder is produced which contains an electrolyte salt and which is a mixture of the following formulas C and D in a molar ratio of about 70 to 30:

≪ RTI ID = 0.0 &

[Chemical Formula D]

b) About 0.2 part of this dye powder is dissolved in 200 parts of water at a temperature of 20 캜. 10 parts of the polyamide fiber fabric described in Example B-1 to be described later is added, the pH is adjusted to 5.5 with dilute aqueous acetic acid if necessary, the fabric is stirred in a water bath for several minutes and then heated to 90 DEG C for 30 minutes. The dyeing process is continued for 45 minutes while maintaining the pH at 5.5. After cooling the bath, the pH is adjusted to about 10.5 and after about 15 minutes the fabric is further shaken to finish dyeing. After removing the fabric from the bath, the finishing treatment is carried out according to the procedure shown in Example 1.

A dyed product of excellent color strength with a clear bright yellow color tone and a high level of saltiness was obtained.

Example 4

65 parts of an electrolytic salt (mostly sodium chloride) containing 31 parts (= 50 molar equivalents) of a dye of the formula (E) and 3.2 parts (= 20 molar equivalents) of a dye powder containing sodium salt of N-methyltaurine was dissolved in 1000 parts of water Is dissolved in 4 parts of trisodium phosphate dissolved solution at 20 占 폚. The resulting dye solution has a pH of 9-10. The mixture was heated to a temperature of about 90 ° C., maintained at the same temperature for about 10 minutes, adjusted to pH 5.5 with aqueous acetic acid having a strength of 50%, and supplemented with water to prepare 5000 parts of skin.

(E)

20 parts of the dye raw material was taken up to 100 parts by adding water containing about 0.2% of a commercially available wetting agent. This bath was added to 10 parts of fabric prepared from the nylon fibers described in Example B-1 and then the pH of the dye bath was adjusted to 5.5 with acetic acid and then the bath was heated continuously to 98 占 폚 for 50 minutes The dyeing process is continued for 45 minutes at the following copper temperature, the bath is cooled to 60 占 폚, the pH is adjusted to 10.5 using a concentrated aqueous sodium hydroxide solution, and the copper pH is maintained at 60 占 폚 for 15 minutes. The bath was then drained, the dyed fabric was rinsed with cold water, washed in an aqueous bath containing non-ionic detergent at a temperature of 80 DEG C, rinsed again at a temperature of 40 DEG C in a bath containing a small amount of acetic acid, Followed by rinsing in cold water, followed by centrifugation and drying.

A dyed product with excellent color strength having a clear and distinct blue hue was obtained. This dye is characterized by high level of saltiness.

Example 5

33 parts (= 33 molar equivalents) of the dye of the formula (F) and 2.4 parts (= 17 molar equivalents) of N-methyltaurine are dissolved in 20 parts of a solution of 10 parts of trisodium phosphate in 1000 parts of water. The resulting dye solution has a pH of about 10. The mixture was heated to a temperature of about 90 ° C, maintained at the same temperature for about 10 minutes, adjusted to pH 5.5 with acetic acid having a strength of 50%, and supplemented with water to make 5000 parts of skin.

[Chemical Formula F]

20 parts of the dye raw material liquid is taken and 100 parts of skin is made by adding water containing about 0.1% of a commercial humectant. The bath was added to 10 parts of fabric prepared from the nylon fibers described in Example B-1, and the pH of the bath was adjusted to 5.5 using acetic acid, and then the bath was heated constantly to 98 DEG C for 30 minutes. The bathing process was continued for 45 minutes at the same temperature, the bath was cooled to 60 占 폚, the pH was adjusted to 10.5 with a concentrated aqueous sodium hydroxide solution, and maintained at this pH and 60 占 폚 for 15 minutes. The bath is then drained and the dyed fabric is finished in the usual manner. In the conventional method, the fabric is rinsed with cold water, washed in an aqueous bath containing a nonionic detergent at a temperature of 80 DEG C, rinsed again in a bath containing a small amount of acetic acid at a temperature of 40 DEG C, Followed by centrifugal separation and drying.

A dyed product of excellent color strength having a clear blue color tone was obtained. This dyeing also showed a high level of saltiness.

Example 6

28 parts (= 50 molar equivalents) of a dye of the formula G and 1.6 parts (= 10 molar equivalents) of N-methyltaurine sodium salt are added to a solution of 7 parts of trisodium phosphate in 1000 parts of water and dissolved do. The resulting dye solution has a pH of about 10. The mixture was heated to a temperature of about 90 ° C., maintained at the same temperature for about 10 minutes, adjusted to pH 5.5 with aqueous acetic acid having a strength of 60%, and supplemented with water to prepare 5000 parts of skin.

[Formula G]

This dye raw material 20 parts Skin was taken and made into 100 parts skin by adding water containing about 0.2% commercial humectant. The bath was added to 10 parts of the fabric prepared from the nylon fiber described later in Example B-1, the pH of the bath was adjusted to 5.5 with acetic acid, the bath was heated to 98 DEG C steadily for 30 minutes, The process was allowed to proceed at the same temperature for 45 minutes, the bath was cooled to 60 ° C, the pH was adjusted to 10.5 with a concentrated aqueous sodium hydroxide solution, and kept at the same pH and 60 ° C for 15 minutes. The bath is then drained and the dyed fabric is finished in the usual manner. In the conventional manner, the dyed fabric is rinsed with cold water, washed in an aqueous bath containing non-ionic detergent at a temperature of 80 DEG C, rinsed again in a bath containing a small amount of acetic acid at a temperature of 40 DEG C, Followed by centrifugal separation and drying.

A dyed product having excellent color strength with a clear and distinct red hue was obtained. This dyeing also has a high level of saltiness.

Example 7

Following the procedure detailed in Example 3a, the two dyes of the formulas H and J and the dye of the formula B are reacted respectively with trisodium phosphate in a separate batch and reacted in a molar ratio of N-methyl React with taurine:

[Formula H] <

[Chemical Formula J]

The dye powders obtained by spray drying from the dyes B, H and J were mixed at a ratio of 20: 10: 6 parts to each other. 10 parts of the polyamide fiber fabric of Example B-1 is dyed similarly to that shown in Example 3b using 0.36 part of this dye mixture. High reddish brown color with high intensity of color is produced with high level of saltiness.

Example 8

According to the procedure described in Example 3a, the dyes of formulas E and H and the dye of formula K are reacted with trisodium phosphate in a separate batch and reacted with N-methyltaurine in the molar ratio shown in Example 3a :

[Chemical formula K]

The dye powders obtained by spray drying from the dyes E, H and K are mixed at a ratio of 5: 5: 8 parts. 10 parts of the polyamide fiber fabric of Example B-1 is dyed similarly to that shown in Example 3b using 0.36 part of this dye mixture. Brown colored dyes with high color intensity and evenness were obtained.

Example 9

23 parts (= 30 molar equivalents) of the dye of the above formula (J) and 1.1 parts (= 12 molar equivalents) of N-methylaminoacetic acid are dissolved in 5 parts of trisphosphate in 1000 parts of water and dissolved at 20 DEG C . The resulting dye solution has a pH of about 10. The mixture was heated to about 90 ° C., kept at the same temperature for about 10 minutes, adjusted to pH 5.5 with acetic acid having a strength of 50%, and supplemented with water to make 5000 parts skin.

The dye raw material liquid 20 parts The skin is taken and water is added to make 100 parts skin. This solution contains about 0.2% commercial wetting agent. The bath was added to 10 parts of fabric prepared from the nylon fibers described in Example B-1, and the pH of the bath was adjusted to 5.5 with acetic acid, and the bath was then heated continuously at 98 占 폚 for 30 minutes. The dyeing process was continued for 45 minutes at the same temperature, the bath was cooled to 60 ° C, the pH was adjusted to 10.5 with a concentrated aqueous sodium hydroxide solution, and kept at the same pH and at 60 ° C for 15 minutes. The bath is then drained and the dyed fabric is finished in the usual manner. In the conventional manner, the dyed fabric is rinsed with cold water, washed in an aqueous bath containing non-ionic detergent at a temperature of 80 DEG C, rinsed again in a bath containing a small amount of acetic acid at a temperature of 40 DEG C, Followed by centrifugal separation and drying.

A dyed product having excellent color strength with a clear and distinct blue hue was obtained. The dyeings also showed a high level of salinity

Example 10

30 parts (= 50 molar equivalents) of the dye of the following formula L and 1.3 parts (= 12.5 molar equivalents) of diethanolamine were dissolved in 20 parts of a solution of 7 parts of trisodium phosphate in 1000 parts of water. The resulting dye solution has a pH of about 10. The mixture was heated to a temperature of about 90 ° C., maintained at the same temperature for about 10 minutes, adjusted to pH 5.5 with acetic acid having a strength of 60%, and supplemented with water to make 5000 parts of skin.

[Chemical formula L]

20 parts of the dye raw material was taken and 100 parts of skin was made by adding water containing about 0.1% of a commercial humectant. The bath was added to 10 parts of fabric prepared from the nylon fibers described in Example B-1 below, the pH of the bath was adjusted to 5.5 with acetic acid, and the bath was heated to 98 DEG C steadily for 30 minutes. The dyeing process was continued for 45 minutes at the same temperature, the bath was cooled to 60 ° C, the pH was adjusted to 10.5 with a concentrated aqueous sodium hydroxide solution, and kept at the same pH and at 60 ° C for 15 minutes. The bath is then drained and the dyed fabric is finished in the usual manner. In the conventional manner, the dyed fabric is rinsed with cold water, washed in an aqueous bath containing non-ionic detergent at a temperature of 80 DEG C, rinsed again in a bath containing a small amount of acetic acid at a temperature of 40 DEG C, Followed by centrifugal separation and drying.

A dyed product with excellent color strength was obtained with a clear and distinct golden orange hue. This dye was much sharper, brighter and thicker than the dye L alone, and exhibited a very high level of saltiness

Example 11

, 91 parts of an electrolyte salt (mainly containing sodium chloride) containing 33 parts (= 33 molar equivalents) of the dye powder containing the dye of the above formula (F), 2.4 parts (= 17 mol equivalents) of N-methyltaurine and 10 parts of trisodium phosphate Was dissolved in 1000 parts of water at 20 占 폚. The resulting dye solution has a pH of about 10. It was heated to a temperature of about 90 ° C and held at that temperature for about 10 minutes and the pH was adjusted to 5.5 with acetic acid having a strength of 50% and then made into 25000 parts skin with water containing 0.1% commercial wetting agent .

The bath was added to 2500 parts of the fabric prepared from the nylon fibers described in Example B-1 below, the pH of the bath was adjusted to 5.5 with acetic acid, and the bath was continuously heated to 98 DEG C for 30 minutes. The dyeing process was continued for 45 minutes at the same temperature, the bath was cooled to 60 ° C, the pH was adjusted to 10.5 with a concentrated aqueous sodium hydroxide solution, and kept at the same pH and at 60 ° C for 15 minutes.

The bath is then drained and the dyed fabric is finished in the usual manner. In the conventional method, the dyed fabric is rinsed with cold water, then washed in an aqueous bath containing non-ionic detergent at a temperature of 80 DEG C, rinsed again in a bath containing a small amount of acetic acid at a temperature of 40 DEG C, Followed by centrifugal separation and drying.

Similar to Example 5, a dyed product having excellent color intensity and high level of saltiness with a clear navy hue was obtained.

Examples 12 to 15

In order to prepare the dye mixtures of the present invention and the polyamide fiber dyeings, the procedures of Examples 1 to 3 or 11 were carried out in the same manner, but instead of the dye A or B or F used in these Examples, Any of the dyes of the following formulas (M) to (P) in the embodiment to be used is used in the molar equivalents used in Examples 1, 2, 3 or 11. In each case, a dye having high color intensity and evenness on the polyamide fabric was obtained and had a clear hue as shown in Tables 1a and 1b below:

[Table 1a]

[Table 1b]

Comparative Example 1

When the procedure according to the embodiment of the above-mentioned table uses only one of the dyes as in the prior art, that is, when one compound of N-methyltaurine or other amino compound corresponding to the formula 3 is not added, But the brightness and sharpness are lowered and some uneven dyeing appears in the individual fiber portions.

Examples 16 to 27

In order to prepare the dye mixtures according to the invention and the polyamide fiber dyeings, the procedures of Examples 1 to 3 or 11 were carried out in the same manner, except that instead of the dye A or B or F used in these examples, One of the dyes shown and the amino compound of formula (3) are used in the molar equivalents given in the examples in Table 2 below. The use of a dyeing agent (B) to form a dye mixture corresponding to Formulas 1 and 2 in the same system results in a dyeing of excellent color strength to a synthetic polyamide fiber fabric, As a suggested color tone, it showed a clear color tone with high level of saltiness.

[Chemical formula (Q)

[Chemical formula R]

[Chemical Formula S]

[Chemical Formula T]

[Chemical Formula U]

(V)

[Formula W]

(X)

[Formula Y]

[Table 2]

Comparative Example 2

When only one of the dyes is used as in the prior art, i.e., when N-methyltaurine or other amino compound corresponding to formula (III) is not added, the dyeing is obtained in the above-described color tone, The sharpness is lowered and some uneven dyeing appears in individual fiber portions.

Example A

Preparation of nylon-6,6 homopolymer

A nylon-6,6 homopolymer was prepared from a 51.5% nylon-6,6 salt aqueous solution (made from hexamethylenediamine and adipic acid) containing 44 ppm defoamer in a stirred vessel. The mixture is heated to a temperature of from room temperature to 155 캜 at an absolute pressure of 2.7 bar and evaporated. The evaporation is stopped at a point having a solids content of 80 to 85%. The concentrated slurry was transferred to autoclave under an inert gas (nitrogen) and the temperature of the mixture was increased by applying heat to the vessel. The autoclave's autogenous pressure is maintained at an absolute pressure of 18.2 bar. 3300 ppm of TiO ₂ 40% aqueous dispersion at 230 ° C and an absolute pressure of 18.2 bar was introduced into the autoclave using a nitrogen pressure of 20 bar. After the pressure of the autoclave was reduced to atmospheric pressure at 245 ° C, a vacuum was applied to the vessel to reduce the absolute pressure to 0.65 and then to maintain it for about 30 minutes. The temperature of the vessel was maintained above the melting temperature of the currently formed polymer, the vacuum was removed and anhydrous nitrogen was introduced to increase the pressure in the vessel to atmospheric pressure. At about 285 DEG C, an absolute pressure of 4 to 5 bar of pressurized nitrogen was introduced into the vessel. Excessive pressure causes the polymer to melt and flow into the flow of cooling water from the vessel opening in lace form. This cooled polymer lace is chopped (granulated). This is cooled with water. The polymer chips (about 4 mm long and 3 mm in diameter) are then removed from the water and dried in air at a temperature below about 60 ° C. The resulting nylon-6,6 homopolymer exhibited a relative viscosity (RV) of 38 to 41 as measured in 90% formic acid, indicating that the amine and carboxy terminus are balanced with respect to each other. The measured amine end groups were typically about 45 g equivalents (measured relative to polymeric polymers known in titration) to 1000 kg of polymer. The polymer thus prepared contained 0.24 to 0.31% titanium dioxide (TiO ₂ ) matting agent.

After the nylon-6,6 homopolymer chips described above were melted in a screw extruder, the molten polymer was introduced into a spinner with 92 openings at 285 DEG C using a pump. The pump carried the polymer at a rate of 0.479 g / opening / minute. The resulting nylon filament was cooled with converging cross-flow air to form a multi-filament, which was oil treated and wound onto a winder, 4 meters below the spinneret at a speed of 4200 meters per minute. The prepared yarn was treated with a combustor to obtain a yarn of 85 denier (0.92 denier per filament) based on 92 filaments. The fabric-woven yarns were braided into a marriage tube for dyeing using the dyeing composition of Example 3 described herein. A color fastness test of the dyeings was carried out at 60 ° C according to ISO CO 6 / C2 using 4 g of ECE detergent and 1 g of sodium perborate per liter of water. As a result, a washing fastness of grade 3 was obtained. The color fastness of the same dye according to ISO EO1 was grade 3.

Example B-1

Preparation of Nylon-6,6 / 6- Copolymer Reinforced with Amine Terminal Groups

A 51.5% aqueous solution of nylon-6,6 salt (made of hexamethylenediamine and adipic acid) was added to a 40% ε-caprolactam aqueous solution at a ratio of 194.000: 35.000 parts, where 86 parts of 30% aqueous hexamethylenediamine solution An excess of diamine was used because the diamine was lost by evaporation) and 10 parts of defoamer. The reaction mixture is transferred to an evaporator, the water is evaporated until the temperature of the evaporator reaches 155 ° C, absolute pressure 2.7 bar, and evaporation is stopped. The concentrated mixture was treated in the same manner as in Example A with respect to the nylon-6,6 homopolymer. The resulting nylon-6,6 / 6-copolymer (85: 15%) had 67 to 73 g equivalents of amine (measured relative to standard polymers known by the titration method) to 1000 kg of polymer, RV Was 52.5 and contained about 0.3% TiO ₂ matting agent.

The resultant nylon polymer was melt-spun according to Example A, using a device with two spinner arrangements, to obtain 60 denier / 68 filaments to be 0.88 denier per filament and 1.69 denier per filament after weaving in the combustor 78 denier / 46 filaments was obtained as much as possible. These yarns were braided and dyed with the dye composition of Example 3, for example, as disclosed herein, to give a color wash fastness rating of 4 to 5 and a fastness rating of 4 in cold water.

Example B-2

Preparation of nylon-6,6 / 6-isophthalic acid copolymer having reinforced amine end groups

A 51.5% aqueous solution of nylon-6,6 salt (made from hexamethylenediamine and adipic acid) was mixed with 97 parts of adipic acid and 10 parts of defoamer from a mixture of hexamethylenediamine and isophthalic acid (iPa) in a ratio of 196,000: 41,400 parts Was added to the 36% aqueous nylon-6, iPa salt solution. The mixture was transferred to an evaporator and treated in the same manner as in Example A. The nylon-6,6 / 6, iPa copolymer (87: 13%) had an amine end group of 67 to 73 g equivalents per 1000 kg of polymer (specified by comparison with standard polymer samples known by titration) Was 55.0 and had 0.3% TiO ₂ matting agent.

The nylon-6,6 / 6, iPa copolymer having the reinforced amine end groups thus obtained was melt-spun and fired under the same conditions as in Example A to give a 58 denier / filament of 0.92 denier / filament based on 92 filaments Of yarn is obtained. When this polymer was spinning using three different spinneret configurations, it was found to be 60 denier / 68 filaments, i.e. 0.88 denier per filament (after texturing in a combustor), 78 denier / 46 filaments, i.e. 1.69 denier per filament after filamentization, And 78 denier / 20 filament, i.e. 3.90 denier per filament. The yarn thus produced is braided and dyed with, for example, the dye composition of Example 3 described above. Color wash fastness rating is 4 to 5 and fastness to cold water is 4 grade.

Example B-3

Preparation of nylon-6 homopolymer with reinforced amine end groups

40% aqueous solution of ε-caprolactam, 400 to 500 ppm of 30% aqueous solution of hexamethylenediamine and 10 parts of defoamer are transferred to an evaporator and water is evaporated at an absolute pressure of 2.7 bar until the temperature of the evaporator reaches 155 ° C. When this temperature is reached, evaporation is terminated. The concentrated mixture is treated as in Example A. The nylon-6 polymer contained 67 to 73 grams of amine per 1000 kg of polymer (determined by comparison with a standard polymer sample known by the titration method), an RV of 52.2, and a 0.3% TiO ₂ matting agent. The chips are melted and spun as described in Example A and then stained with the dye composition of the present invention, for example, the composition of Example 3. In this case, the dyeings had a color wash fastness rating of 4 to 5 and a fastness rating of 4 in cold water.

The dye composition according to the present invention can dye synthetic polyamide fibers and the like with high fastness and balanced saltiness without changing color tone at the beginning and end of dyeing.

Claims (3)

A dye of formula (1), wherein the dye of formula ( ₂ ) is - (SO ₂ -CH═CH ₂ ) _n and - [SO ₂ -CH dyeing composition present in a molar equivalent ratio of _{40%: 2 -CH 2 -N (} R) -VX] a group of standard _n 90: 10% to 60: Formula 1 (2) In the above equations, F is the same as in Formulas 1 and 2 and is a mono-, dis- or polyazo dye, or a heavy metal complex mono-, dis- or trisazo dye, or anthraquinone, azomethine, phenazine, stilbene, triphenylmethane As radicals of dyes, such as xanthene, thioxanthene, nitroaryl, naphthoquinone, perylenetetracarbimide, formazan, copper formazan, phthalocyanine, copper phthalocyanine, nickel phthalocyanine or cobalt phthalocyanine dyes, , Which have one or two groups which impart water-solubility such as sulfato, sulfo and carboxy groups; n is 1 or 2; M is hydrogen or an alkali metal; R is hydrogen or an alkyl of 1 to 6 carbon atoms which may be interrupted by one or two hetero groups and is selected from the group consisting of sulfo, carboxy, hydroxy, sulfato, phosphato and alkanoylamino of 2 to 5 carbon atoms Lt; / RTI >; V is a covalent bond, alkylene of 1 to 4 carbon atoms, or the following structural formula _{-CO-NH-CH 2 -CH 2} - is a group of; X is a group which imparts water-solubility. And at least one dye selected from the group consisting of dyes represented by the following formula (1A) and dyes represented by the following formula (1), and one or more compounds represented by the following formula (3) Wherein the dye is present in a molar equivalent ratio of 100: 10% to 100: 40% based on the ethylsulfonyl group and the vinylsulfonyl group: ≪ Formula 1 (3) In the above equations, F is a mono-, di- or polyazo dye (e.g. trisazo dye), or a heavy metal complex mono-, dis- or trisazo dye, or anthraquinone, azomethine, phenazine, stilbene, triphenylmethane, As radicals of dyes, such as xanthene, thioxanthene, nitroaryl, naphthoquinone, perylenetetracarbimide, formazan, copper formazan, phthalocyanine, copper phthalocyanine, nickel phthalocyanine or cobalt phthalocyanine dyes, Sulfo, sulfo, and carboxyl groups; and < RTI ID = 0.0 > R < / RTI > n is 1 or 2; M is hydrogen or an alkali metal; R is hydrogen or an alkyl of 1 to 6 carbon atoms which may be interrupted by one or two hetero groups and is selected from the group consisting of sulfo, carboxy, hydroxy, sulfato, phosphato and alkanoylamino of 2 to 5 carbon atoms ≪ / RTI > V is a covalent bond, alkylene of 1 to 4 carbon atoms, or the following structural formula _{-CO-NH-CH 2 -CH 2} - is a group of; X is a group which imparts water-solubility. 3. The method of claim 2, Wherein R is methyl or ethyl.